CN111171232A - Polymer, preparation method and application thereof, and drilling fluid containing polymer - Google Patents
Polymer, preparation method and application thereof, and drilling fluid containing polymer Download PDFInfo
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Abstract
The invention relates to the technical field of oil and gas drilling, and discloses a polymer, a preparation method and application thereof, and a water-based drilling fluid containing the polymer, wherein the polymer contains a structural unit A, a structural unit B and a structural unit C, and the structural unit A is at least one selected from structural units with a structure shown in a formula (11), a structure shown in a formula (12) and a structure shown in a formula (13); the structural unit B is a structural unit with a structure shown in a formula (2); the structural unit C is at least one selected from structural units having a structure represented by formula (31) and a structure represented by formula (32); the weight average molecular weight of the polymer is 35-60 ten thousand, and when the polymer provided by the invention is used for a drilling fluid dispersing agent, the polymer can be used forCan realize good hydration dispersion in a high-calcium environment, play a good role in dispersion and improve the thermal stability of the drilling fluid.
Description
Technical Field
The invention relates to the technical field of oil and gas drilling, in particular to a polymer, a method for preparing the polymer, the polymer prepared by the method, application of the polymer in drilling fluid and the drilling fluid containing the polymer.
Background
The drilling fluid is a circulating flushing medium used in the drilling process, is called as the 'blood' of the drilling, has multiple functions of suspending and carrying drill cuttings, preventing borehole wall collapse, protecting oil and gas reservoirs, cooling and lubricating drilling tools, transferring pump power, recording geological data and the like, and is an important factor influencing the success or failure of the drilling and the drilling speed.
For water-based drilling fluids, calcium resistance is one of the technical problems which need to be solved urgently, and the calcium resistance is not solved well for a long time. The 'dehydration' action of calcium ions can compress the diffusion double electric layers of colloids such as clay and the like, so that the problems of excessive flocculation, great increase of viscosity and shearing force, rapid increase of filtration loss and the like of the drilling fluid are caused, and the water-based drilling fluid can not be normally used seriously.
In order to combat the problem of calcium invasion in water-based drilling fluids, researchers have found that the use of dispersants with strongly hydrated groups such as sulfonated phenolic resins, sulfonated tannins, and the like, in water-based drilling fluids is one of the effective methods. However, the method has the defects that the environmental protection performance of the dispersing agent is poor, and the dispersing agent is easy to lose effectiveness in a high-concentration calcium ion environment. In addition, although the polymer dispersant has good dispersing performance, environmental protection performance and the function of reducing the filtration loss, most polymers are easy to be aggregated and precipitated by calcium ions after being ionized in the drilling fluid, so that the solubility is poor and even the polymer dispersant is ineffective, and the polymer dispersant is particularly serious under the high-temperature condition.
Therefore, the development of a new dispersing agent capable of realizing effective dispersion of the high-calcium water-based drilling fluid has important practical significance.
Disclosure of Invention
The invention aims to overcome the defects of over flocculation, large filtration loss and poor dispersibility in the high-calcium water-based drilling fluid in the prior art due to the dehydration effect of calcium ions.
In order to achieve the above object, the first aspect of the present invention provides a polymer comprising a structural unit A, a structural unit B and a structural unit C,
the structural unit A is at least one structural unit selected from the group consisting of a structural unit having a structure represented by formula (11), a structural unit having a structure represented by formula (12), and a structural unit having a structure represented by formula (13); the structural unit B is a structural unit with a structure shown in a formula (2); the structural unit C is at least one selected from structural units having a structure represented by formula (31) and a structure represented by formula (32); the weight average molecular weight of the polymer is 35-60 ten thousand;
wherein the content of the first and second substances,
in the formulae (11), (12) and (13), R11、R12、R13、R15And R16Each independently selected from H and C1-C4 alkyl, R14Selected from C1-C4 alkylene, M1、M2、M3Each independently is Na or K;
in the formula (2), R21And R22Each independently selected from C1-C4 alkyl, X-Selected from Cl-、Br-And I-；
In the formulae (31) and (32), R31And R32Each independently selected from C1-C4 alkyl, R33Selected from H and C1-C4 alkyl, t1, t2 and t3 are each independently integers of 1-6.
In a second aspect the present invention provides a process for the preparation of a polymer, which process comprises:
carrying out polymerization reaction on each component in a polymerization composition in the presence of a cosolvent, a chain transfer agent and an initiator in an aqueous solvent and a protective atmosphere, wherein the polymerization composition contains a monomer A ', a monomer B ' and a monomer C ';
the monomer A' is at least one monomer selected from the group consisting of a monomer having a structure represented by formula (I1), a monomer having a structure represented by formula (I2), and a monomer having a structure represented by formula (I3); the monomer B' is a monomer with a structure shown in a formula (II); the monomer C' is at least one selected from monomers having a structure represented by formula (III1) and a structure represented by formula (III 2);
the monomer A ', the monomer B ' and the monomer C ' are respectively used for leading the polymer to contain a structural unit A, a structural unit B and a structural unit C, wherein the structural unit A is at least one selected from structural units with a structure shown in a formula (11), a structure shown in a formula (12) and a structure shown in a formula (13); the structural unit B is a structural unit with a structure shown in a formula (2); the structural unit C is at least one selected from structural units having a structure represented by formula (31) and a structure represented by formula (32); the amount of the polymeric composition used is such that the resulting polymer has a weight average molecular weight of from 35 to 60 million;
wherein, the definition of each group is the same as that of the previous group.
In a third aspect, the present invention provides a polymer obtainable by the process of the second aspect described above.
In a fourth aspect the present invention provides the use of a polymer according to the first or third aspects above in a drilling fluid.
In a fifth aspect, the present invention provides a drilling fluid comprising a polymer according to the first or third aspects above.
The polymer provided by the invention has at least the following advantages:
(1) when the polymer provided by the invention is used for a water-based drilling fluid dispersing agent, the polymer has good compatibility with calcium salt, can maintain good hydration dispersion in a high-calcium environment, can be preferentially adsorbed to bentonite, weakens the dehydration effect of calcium ions on the bentonite, plays a good dispersing role, reduces the filtration loss of the water-based drilling fluid and improves the stability of the drilling fluid;
(2) the polymer provided by the invention has lower molecular weight and unobvious tackifying effect, so that the polymer can be used in large quantities to disperse the drilling fluid and cope with the conditions of high calcium and ultrahigh calcium of the water-based drilling fluid;
(3) the preparation method provided by the invention can obtain a high-concentration polymer solution, the polymer solution can be directly utilized after synthesis, no post-treatment is needed, the dispersion is easy to realize during use, and the preparation efficiency of the drilling fluid can be improved.
Additional features and advantages of the invention will be described in detail in the detailed description which follows.
Drawings
FIG. 1 is an infrared spectrum of the polymer prepared in example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the invention, the alkyl of C1-C4 refers to the alkyl with 1-4 carbon atoms; the alkylene group having C1-C4 means an alkylene group having 1-4 carbon atoms. Integers from 1 to 6 include 1, 2, 3, 4, 5 and 6, and integers from 1 to 5 include 1, 2, 3, 4 and 5.
In the present invention, the alkyl group of C1-C4 may include, but is not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.
In the present invention, the alkylene group refers to a residue of an alkane which has been deprived of two hydrogen atoms, which may be two hydrogen atoms on the same carbon atom or two hydrogen atoms on different carbon atoms, and which may be linear or branched, for example, the ethylene group may be-CH2CH2-or-CH (CH)3)-。
In the present invention, the alkylene group of C1-C4 may include, but is not limited to: methylene, ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, isobutylene, tert-butylene.
In the present invention, the alkylene group of C1-C3 may include, but is not limited to: methylene, ethylene, n-propylene, isopropylene.
As described above, the first aspect of the present invention provides a polymer comprising a structural unit A, a structural unit B and a structural unit C,
the structural unit A is at least one structural unit selected from the group consisting of a structural unit having a structure represented by formula (11), a structural unit having a structure represented by formula (12), and a structural unit having a structure represented by formula (13); the structural unit B is a structural unit with a structure shown in a formula (2); the structural unit C is at least one selected from structural units having a structure represented by formula (31) and a structure represented by formula (32); the weight average molecular weight of the polymer is 35-60 ten thousand;
wherein the content of the first and second substances,
in the formulae (11), (12) and (13), R11、R12、R13、R15And R16Each independently selected from H and C1-C4 alkyl, R14Selected from C1-C4 alkylene, M1、M2、M3Each independently is Na or K;
in the formula (2), R21And R22Each independently selected from C1-C4 alkyl, X-Selected from Cl-、Br-And I-；
In the formulae (31) and (32), R31And R32Each independently selected from C1-C4 alkyl, R33Selected from H and C1-C4 alkyl, t1, t2 and t3 are each independently integers of 1-6.
According to a preferred embodiment of the present invention, in the formulae (11), (12) and (13), R11、R12、R13、R15And R16Each independently selected from H, methyl, ethyl, n-propyl and isopropyl, R14Selected from C1-C3 alkylene, M1、M2、M3Each independently is Na or K;
in the formula (2), R21And R22Each independently selected from methyl, ethyl, n-propyl and isopropyl, X-Is Cl-Or Br-；
In the formulae (31) and (32), R31、R32And R33Each independently selected from methyl, ethyl, n-propyl and isopropyl, and t1, t2 and t3 each independently is an integer from 1 to 5.
According to another more preferred embodiment of the present invention, the structural unit a is at least one selected from the group consisting of structural units having a structure represented by formula (14), a structure represented by formula (15) and a structure represented by formula (16); the structural unit B is a structural unit with a structure shown in a formula (4); the structural unit C is at least one structural unit selected from the group consisting of a structural unit having a structure represented by formula (51), a structural unit having a structure represented by formula (52), and a structural unit having a structure represented by formula (53);
preferably, the content of the structural unit A is 53.4 to 84.6 wt% based on the total weight of the polymer; the content of the structural unit B is 8.2-25.0 wt%; the content of the structural unit C is 7.1-21.6 wt%, so that the polymer has more excellent dispersing performance when used for water-based drilling fluid, and the obtained water-based drilling fluid has better calcium resistance and higher stability.
In order to obtain a water-based drilling fluid with better calcium resistance when used in the water-based drilling fluid, the weight average molecular weight of the polymer is preferably 40-60 ten thousand.
As previously mentioned, a second aspect of the invention provides a method of preparing a polymer, the method comprising:
carrying out polymerization reaction on each component in a polymerization composition in the presence of a cosolvent, a chain transfer agent and an initiator in an aqueous solvent and a protective atmosphere, wherein the polymerization composition contains a monomer A ', a monomer B ' and a monomer C ';
the monomer A' is at least one monomer selected from the group consisting of a monomer having a structure represented by formula (I1), a monomer having a structure represented by formula (I2), and a monomer having a structure represented by formula (I3); the monomer B' is a monomer with a structure shown in a formula (II); the monomer C' is at least one selected from monomers having a structure represented by formula (III1) and a structure represented by formula (III 2);
the monomer A ', the monomer B ' and the monomer C ' are respectively used for leading the polymer to contain a structural unit A, a structural unit B and a structural unit C, wherein the structural unit A is at least one selected from structural units with a structure shown in a formula (11), a structure shown in a formula (12) and a structure shown in a formula (13); the structural unit B is a structural unit with a structure shown in a formula (2); the structural unit C is at least one selected from structural units having a structure represented by formula (31) and a structure represented by formula (32); the amount of the polymeric composition used is such that the resulting polymer has a weight average molecular weight of from 35 to 60 million;
wherein the definitions of the radicals correspond to the above definitions.
In the method according to the second aspect of the present invention, the monomer having a structure represented by formula (I1), the monomer having a structure represented by formula (I2), the monomer having a structure represented by formula (I3), the monomer having a structure represented by formula (II), the monomer having a structure represented by formula (III1), and the monomer having a structure represented by formula (III 2); and the definitions and material types of the substituents in the structural unit of the structure shown in the formula (11), the structural unit of the structure shown in the formula (12), the structural unit of the structure shown in the formula (13), the structural unit of the structure shown in the formula (2), the structural unit of the structure shown in the formula (31) and the structural unit of the structure shown in the formula (32) are the same as the definitions and material types of the substituents described above, and are not repeated herein, and a person skilled in the art should not be construed as a limitation to the technical scheme of the present invention.
In the present invention, the monomer a ', the monomer B ' and the monomer C ' may be obtained commercially, or may be synthesized according to the structural formula provided in the present invention in combination with a known method in the field of organic synthesis.
In the present invention, it is to be noted that the monomer is converted almost completely into the corresponding structural unit contained in the polymer, and the amount of the monomer to be used may be the same as the content of the corresponding structural unit contained in the polymer.
In order to obtain a polymer with more excellent dispersion performance when used in a water-based drilling fluid, the monomer A' is preferably at least one monomer selected from the group consisting of monomers having a structure represented by formula (I4), a structure represented by formula (I5), and a structure represented by formula (I6); the monomer B' is a monomer with a structure shown in a formula (IV); the monomer C' is at least one selected from the group consisting of monomers having a structure represented by formula (V1), a structure represented by formula (V2), and a structure represented by formula (V3);
preferably, the monomers A ', B ' and C ' are used in such amounts that the resulting polymer has a content of structural units A of from 53.4 to 84.6% by weight, based on the total weight of the polymer; the content of the structural unit B is 8.2-25.0 wt%; the content of the structural unit C is 7.1-21.6 wt%, so that the prepared polymer has more excellent dispersing performance when used for water-based drilling fluid, and the obtained water-based drilling fluid has better calcium resistance and higher stability.
In order to obtain a water-based drilling fluid with better calcium resistance when used in a water-based drilling fluid, the polymeric composition is preferably used in an amount such that the resulting polymer has a weight average molecular weight of from 40 to 60 ten thousand.
Preferably, the co-solvent is selected from at least one of soluble salts, more preferably, the co-solvent is selected from at least one of ammonium chloride, sodium chloride and potassium chloride.
Preferably, the chain transfer agent is selected from at least one of sodium formate, potassium formate, sodium acetate and potassium acetate.
Preferably, the initiator is selected from at least one of azo-type initiators, peroxide-type initiators, and redox-type initiators; the azo initiator is selected from at least one of azobisisobutyramidine hydrochloride, azobisisopropylimidazoline hydrochloride, azobiscyanovaleric acid and azobisisopropylimidazoline; the peroxide initiator is at least one selected from hydrogen peroxide, ammonium persulfate, sodium persulfate and potassium persulfate; the redox initiator is selected from at least one of persulfate-sulfite, persulfate-thiourea and persulfate-organic salt, and more preferably, the initiator is selected from potassium persulfate and/or azodiisobutymidine hydrochloride.
In the present invention, the chain transfer agent is used in an amount of 0.2 to 0.3% by weight and the initiator is used in an amount of 0.3 to 0.5% by weight, based on the total amount of the polymerization composition.
In the present invention, the aqueous solvent may be pure distilled water and/or deionized water, or may be a mixed solvent containing distilled water and/or deionized water.
Preferably, the polymeric composition is used in an amount of 30 to 50% by weight based on the amount of the aqueous solvent.
Preferably, the co-solvent is used in an amount of 8 to 10 wt% based on the amount of the aqueous solvent.
Preferably, the polymerization conditions include: the temperature is 45-75 ℃, and the time is 7-10 h.
In the present invention, the polymerization reaction is carried out under a protective atmosphere, which is preferably nitrogen.
In the present invention, according to a preferred embodiment, the method for preparing the polymer comprises the following steps:
(1) adding the monomer A ', the monomer B ' and the monomer C ' into a three-neck flask containing distilled water, and stirring until the monomers are uniformly mixed, wherein the total amount of the monomers is 30-50 wt% based on the amount of the distilled water;
(2) adding a cosolvent, a chain transfer agent and an initiator into the aqueous solution obtained in the step (1), and uniformly stirring;
(3) and after the addition is finished, sealing the three-neck flask, adding a nitrogen introducing device, introducing nitrogen into the three-neck flask, fully removing air in the flask, heating to 45-75 ℃ for polymerization reaction for 7-10h, and cooling to room temperature after the reaction is finished to obtain a solution containing the polymer.
The preparation method provided by the invention can obtain a high-concentration polymer solution, the polymer solution can be directly used after synthesis, no post-treatment is needed, the dispersion is easy to realize during use, and the preparation efficiency of the drilling fluid can be improved.
As mentioned above, a third aspect of the present invention provides a polymer obtainable by the process of the second aspect described above.
As mentioned above, a fourth aspect of the present invention provides the use of a polymer according to the first or third aspect described above in a drilling fluid.
In the present invention, preferably, the application is the use of the polymer as a dispersant for water-based drilling fluids.
In the use of the above-mentioned polymers as dispersants for water-based drilling fluids, the specific application method is well known to those skilled in the art, and the present invention will not be described herein.
When the polymer is used as a dispersant of water-based drilling fluid, the 'dehydration effect' of calcium ions on bentonite can be weakened, a good dispersing effect is achieved, the filtration loss of the water-based drilling fluid is reduced, and the stability of the drilling fluid is improved; meanwhile, the polymer has a small tackifying effect, can be used in a large amount to cope with the high calcium condition of the water-based drilling fluid, and plays an excellent dispersing role.
In a fifth aspect, the present invention provides a drilling fluid comprising a polymer as described in the first or third aspects above.
Preferably, the drilling fluid is a water-based drilling fluid and the polymer is used as a dispersant in the water-based drilling fluid.
According to a preferred embodiment of the invention, the drilling fluid further comprises bentonite, calcium chloride, white bitumen, barite and water.
Preferably, in the drilling fluid, relative to 100 parts by weight of water, the content of the bentonite is 1-2 parts by weight, the content of the calcium chloride is 10-15 parts by weight, the content of the white asphalt is 1-3 parts by weight, the content of the barite is 150-180 parts by weight, and the content of the polymer is 2.5-3 parts by weight.
In the present invention, there is no particular limitation on the preparation method of the drilling fluid, and the preparation method known to those skilled in the art can be adopted, and the present invention is not described herein again, and the present invention is described in detail in the following, and those skilled in the art should not be construed as limiting the present invention.
In the present invention, room temperature means 25. + -. 5 ℃ unless otherwise specified.
In the present invention, the amount of the polymer is not particularly limited, and when the amount is used, the amount is based on the dry weight of the polymer.
The present invention will be described in detail below by way of examples. In the following examples, all the raw materials used are commercially available ones unless otherwise specified.
In the following examples, the test methods for the properties involved are as follows:
1. observation of appearance state of polymer: observation by naked eyes under natural light conditions;
2. structural testing of the polymers: the infrared spectrum test is carried out for characterization to obtain the compound;
3. evaluation of Polymer Dispersion Properties: the dispersion performance of the polymer is evaluated by high-calcium bentonite-based slurry, the high-calcium bentonite-based slurry contains water, bentonite and calcium chloride, and the formula of the high-calcium bentonite-based slurry is as follows: 100 parts by weight of water, 4 parts by weight of bentonite and 4 parts by weight of calcium chloride, and the concrete process is as follows:
taking 300mL of high-calcium bentonite-based slurry, adding 1.5 parts by weight of polymer relative to 100 parts by weight of water, and stirring at a high speed of 3000r/min for 10min by using a stirrer to obtain the drilling fluid-based slurry.
3.1 viscosity determination: the viscosity index improver is obtained by testing a six-speed viscometer model ZNN-D6B of Qingdao Tongchun Petroleum instruments company at room temperature, and specifically comprises the following steps: and pouring the drilling fluid base slurry into a viscosity measuring cup, and sequentially reading phi 6 and phi 3 by using a six-speed viscometer at room temperature.
3.2 measurement of filtration loss: the drilling fluid loss rate tester is obtained by testing a drilling fluid loss rate tester of the Qingdao Tongchun petroleum instrument company SD6 model, and specifically comprises the following steps: pouring the drilling fluid base slurry into a filtration loss measuring cup, adding a sealing ring and covering API filter paper, introducing nitrogen after sealing by using a filter screen, measuring the total volume of filtrate of the drilling fluid base slurry within 7.5min by using a drilling fluid water loss measuring instrument under the pressure of 0.69MPa, and multiplying by 2 to obtain the API Filtration Loss (FL) of the drilling fluid base slurryAPI)。
4. Evaluation of Water-based drilling fluid Performance
The polymers obtained in the following examples were formulated into water-based drilling fluids, and the properties of the water-based drilling fluids were evaluated as follows: 100 parts by weight of water, 1 part by weight of bentonite, 3 parts by weight of polymer, 15 parts by weight of calcium chloride, 3 parts by weight of white asphalt and 150 parts by weight of barite.
The preparation process of the water-based drilling fluid comprises the following steps: sequentially adding bentonite, polymer, calcium chloride, white asphalt and barite into water, and stirring for 5-10min by using a high-speed stirrer after adding one raw material until the raw materials are uniformly dispersed at the stirring speed of 10000-12000rpm to obtain the water-based drilling fluid.
4.1 viscosity determination: the Apparent Viscosity (AV), the Plastic Viscosity (PV), the dynamic shear force (YP), phi 6, phi 3, the initial cut and the final cut of the water-based drilling fluid are measured by using a six-speed viscometer, and the specific method is as follows:
pouring the water-based drilling fluid into a viscosity measuring cup, and sequentially reading phi 600, phi 300, phi 6 and phi 3 by using a six-speed viscometer at room temperature.
AV is calculated as follows:
AV＝0.5×φ600
PV is calculated as follows:
PV＝φ600-φ300
YP was calculated as follows:
YP＝0.51×(2×φ300-φ600)
the initial cut is calculated according to the following method: stirring at 600r/min for 10s, standing for 10s, taking the maximum reading of phi 3, and dividing the maximum reading by 2 to obtain an initial cut.
The final cut is calculated as follows: stirring at a speed of 600r/min for 10s, standing for 10min, taking the maximum reading of phi 3, and dividing the maximum reading by 2 to obtain the final cut.
4.2 temperature resistance measurement: the temperature resistance of the water-based drilling fluid is evaluated by using a roller heating furnace, and the specific method comprises the following steps:
and (3) aging the drilling fluid after the viscosity test is finished in a roller heating furnace at 150 ℃ for 16h, cooling to room temperature after aging, and measuring AV, PV, YP, phi 6 and phi 3, initial cutting and final cutting of the aged water-based drilling fluid according to a method of 3.1.
4.3 high-temperature high-pressure filtration loss measurement: the high-temperature high-pressure Filtration Loss (FL) of the water-based drilling fluid is measured by a drilling fluid high-temperature high-pressure water loss measuring instrument of GGS42-2A model of Qingdao Tongchun oil instrumentsHTHP) The specific method comprises the following steps:
adding the aged water-based drilling fluid into a high-temperature high-pressure filtration loss measuring cup, covering filter paper, sealing a filter screen, introducing 0.7MPa of nitrogen back pressure, and pressurizing to 4.2MPa after the temperature of the instrument is raised to 150 ℃. Keeping the pressure in the measuring cup unchanged at 3.5MPa, testing the total volume of the filtrate of the water-based drilling fluid within 30min, and multiplying by 2 to obtain FLHTHP。
In the following examples, 5g is represented per part by weight unless otherwise specified.
Example 1
(1) Adding a polymer composition (of 58.32g of monomer A ', 15.12g of monomer B' and 6.56g of monomer C ') into a three-neck flask containing 200g of distilled water, heating in a water bath at 25 ℃, and stirring until the monomers are uniformly mixed, wherein the monomer A' is sodium 2-acrylamido-2-methylpropanesulfonate with a structure shown in a formula (I4); the monomer B' is diallyl dimethyl ammonium chloride with a structure shown in a formula (IV); the monomer C' is methacryloyl ethyl sulfobetaine with a structure shown in a formula (V1);
(2) adding 20g of sodium chloride, 0.24g of sodium formate and 0.4g of potassium persulfate into the aqueous solution obtained in the step (1), and uniformly stirring;
(3) after the addition, the three-neck flask was sealed, a nitrogen introducing device was added to introduce nitrogen into the three-neck flask, the air in the flask was sufficiently removed, the temperature was raised to 70 ℃, polymerization was carried out at constant temperature for 8 hours, and after the reaction was completed, cooling was carried out to room temperature, thereby obtaining polymer S1.
The content of the structural unit A in the polymer S1 is 72.9 wt% based on the total weight of the polymer S1; the content of the structural unit B was 18.9 wt%; the content of the structural unit C is 8.2 wt%, and the weight average molecular weight is 55 ten thousand.
Examples 2 to 3
A polymer was prepared in a similar manner to example 1, except that: the polymers S2 and S3 were obtained, respectively, in the same manner as in example 1, except that the type of the monomer A' used was different:
example 2: the same mass of the monomer A 'having a structure represented by the formula (I5) was used in place of the monomer A' in example 1 to obtain a polymer S2;
the content of the structural unit A in the polymer S2 is 72.9 wt% based on the total weight of the polymer S2; the content of the structural unit B was 18.9 wt%; the content of the structural unit C was 8.2% by weight, and the weight average molecular weight was 51 ten thousand.
Example 3: the same mass of the monomer A 'having a structure represented by the formula (I6) was used in place of the monomer A' in example 1 to obtain a polymer S3;
the content of the structural unit A in the polymer S3 is 72.9 wt% based on the total weight of the polymer S3; the content of the structural unit B was 18.9 wt%; the content of the structural unit C is 8.2 wt%, and the weight average molecular weight is 48 ten thousand.
Examples 4 to 6
A polymer was prepared in a similar manner to example 1, except that: the amounts of the monomers used were varied and the rest was the same as in example 1, yielding polymers S4, S5, S6, respectively, in particular:
example 4: the amount of sodium 2-acrylamido-2-methylpropanesulfonate having the structure represented by formula (I4) was 67.68g, the amount of diallyldimethylammonium chloride having the monomer B 'of the structure represented by formula (IV) was 6.56g, and the amount of methacryloylethylsulfonylbine having the monomer C' of the structure represented by formula (V1) was 5.68g, to give polymer S4;
the content of the structural unit A in the polymer S4 is 84.7 wt% based on the total weight of the polymer S4; the content of the structural unit B is 8.2 wt%; the content of the structural unit C was 7.1% by weight, and the weight average molecular weight was 60 ten thousand.
Example 5: the amount of sodium 2-acrylamido-2-methylpropanesulfonate having the structure represented by formula (I4) was 42.72g, the amount of diallyldimethylammonium chloride having the monomer B 'of the structure represented by formula (IV) was 20g, and the amount of methacryloylethyl sulfobetaine having the monomer C' of the structure represented by formula (V1) was 17.28g, to give polymer S5;
the content of the structural unit A in the polymer S5 is 53.4 wt% based on the total weight of the polymer S5; the content of the structural unit B is 25.0 wt%; the content of the structural unit C was 21.6% by weight, and the weight average molecular weight was 44 ten thousand.
Example 6
The amount of sodium 2-acrylamido-2-methylpropanesulfonate having the structure represented by formula (I4) was 35.6g, the amount of diallyldimethylammonium chloride having the monomer B 'of the structure represented by formula (IV) was 24g, and the amount of methacryloylethyl sulfobetaine having the monomer C' of the structure represented by formula (V1) was 20.4g, to give polymer S6;
the content of the structural unit A in the polymer S6 is 44.5 wt% based on the total weight of the polymer S6; the content of the structural unit B is 30 wt%; the content of the structural unit C is 25.5 wt%, and the weight average molecular weight is 39 ten thousand.
Comparative example 1
This comparative example was carried out in a similar manner to example 1, except that in this comparative example, the methacryloylethylsulfonylbine having the structure represented by formula (V1), i.e., the monomer C' in example 1 was not added, to give a polymer DS 1;
the content of the structural unit A in the polymer DS1 is 79.4 wt% based on the total weight of the polymer DS 1; the content of the structural unit B was 20.6% by weight, and the weight average molecular weight was 57 ten thousand.
Comparative example 2
This comparative example was conducted in a similar manner to example 1 except that in this comparative example, sodium 2-acrylamido-2-methylpropanesulfonate represented by formula (I4), that is, monomer A' in example 1 was not added, to obtain polymer DS 2;
the content of the structural unit B in the polymer DS2 is 69.8 percent by weight based on the total weight of the polymer DS 2; the content of the structural unit C is 30.2 wt%, and the weight average molecular weight is 31 ten thousand.
Test example
1. Structural testing
The IR spectra of the polymers prepared in the above examples were tested and the invention illustratively provides an IR spectrum of polymer S1 prepared in example 1, as shown in FIG. 1.
2. Observation of appearance State of Polymer
The appearance of the polymer solution obtained in the above example was recorded and the specific observations are given in table 1.
TABLE 1
| Examples of the invention | Observation of appearance |
| Example 1 | Light yellow liquid |
| Example 2 | Light yellow liquid |
| Example 3 | Light yellow liquid |
| Example 4 | Light yellow liquid |
| Example 5 | Light yellow liquid |
| Example 6 | Light yellow liquid |
| Comparative example 1 | Light yellow liquid |
| Comparative example 2 | Colourless liquid |
3. Evaluation of Polymer Dispersion Properties
The polymers obtained in the examples were formulated into drilling fluid base slurries as described above, and the drilling fluid base slurries were tested for phi 6, phi 3 and API Fluid Loss (FLAPI), with the specific results shown in table 2.
TABLE 2
4. Evaluation of Water-based drilling fluid Performance
The polymers prepared in the above examples are prepared into water-based drilling fluids, which are respectively marked as L1, L2, L3, L3, L5, L6, DL1 and DL2, and the viscosity, the temperature resistance and the high-temperature high-pressure filtration loss of each water-based drilling fluid are tested, and the specific results are shown in Table 3.
TABLE 3
Wherein, for the drilling fluid, AV is apparent viscosity, the larger AV represents the higher viscosity of the system, and the larger molecular weight of the reflecting polymer is;
PV is plastic viscosity, and the larger PV represents the stronger friction effect in the drilling fluid;
YP is dynamic shear force, and the larger the YP is, the stronger the grid structure of the internal space is when the drilling fluid flows;
the larger the initial cutting and the final cutting are, the stronger the internal space grid structure is when the drilling fluid is in standing, and the dispersion of the drilling fluid is reflected to be poor;
greater API fluid loss and high temperature high pressure fluid loss indicate poorer fluid loss wall build of the drilling fluid.
The results show that when the polymer provided by the invention is used for a water-based drilling fluid dispersing agent, the polymer has good compatibility with calcium salt, can maintain good hydration dispersion of the drilling fluid in a high-calcium environment, plays good roles in deflocculation and fluid loss reduction, and the obtained drilling fluid has good thermal stability.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (13)
1. A polymer comprising a structural unit A, a structural unit B and a structural unit C,
the structural unit A is at least one structural unit selected from the group consisting of a structural unit having a structure represented by formula (11), a structural unit having a structure represented by formula (12), and a structural unit having a structure represented by formula (13); the structural unit B is a structural unit with a structure shown in a formula (2); the structural unit C is at least one selected from structural units having a structure represented by formula (31) and a structure represented by formula (32); the weight average molecular weight of the polymer is 35-60 ten thousand;
wherein the content of the first and second substances,
in the formulae (11), (12) and (13), R11、R12、R13、R15And R16Each independently selected from H and C1-C4 alkyl, R14Selected from C1-C4 alkylene, M1、M2、M3Each independently is Na or K;
in the formula (2), R21And R22Each independently selected from C1-C4 alkyl, X-Selected from Cl-、Br-And I-；
In the formulae (31) and (32), R31And R32Each independently selected from C1-C4 alkyl, R33Selected from H and C1-C4 alkyl, t1, t2 and t3 are each independently integers of 1-6.
2. The polymer of claim 1, wherein,
in the formulae (11), (12) and (13), R11、R12、R13、R15And R16Each independently selected from H, methyl, ethyl, n-propyl and isopropyl, R14Selected from C1-C3 alkylene, M1、M2、M3Each independently is Na or K;
in the formula (2), R21And R22Each independently selected from methyl, ethyl, n-propyl and isopropyl, X-Is Cl-Or Br-；
In the formulae (31) and (32), R31、R32And R33Each independently selected from methyl, ethyl, n-propyl and isopropyl, and t1, t2 and t3 each independently is an integer from 1 to 5.
3. The polymer according to claim 1 or 2, wherein the structural unit a is at least one selected from the group consisting of structural units having a structure represented by formula (14), a structure represented by formula (15), and a structure represented by formula (16); the structural unit B is a structural unit with a structure shown in a formula (4); the structural unit C is at least one structural unit selected from the group consisting of a structural unit having a structure represented by formula (51), a structural unit having a structure represented by formula (52), and a structural unit having a structure represented by formula (53);
4. the polymer of any one of claims 1-3, wherein the structural unit A is present in an amount of 53.4 to 84.6 wt%, based on the total weight of the polymer; the content of the structural unit B is 8.2-25 wt%; the content of the structural unit C is 7.1-21.6 wt%;
preferably, the weight average molecular weight of the polymer is from 40 to 60 ten thousand.
5. A method of making a polymer, the method comprising:
carrying out polymerization reaction on each component in a polymerization composition in the presence of a cosolvent, a chain transfer agent and an initiator in an aqueous solvent and a protective atmosphere, wherein the polymerization composition contains a monomer A ', a monomer B ' and a monomer C ';
the monomer A' is at least one monomer selected from the group consisting of a monomer having a structure represented by formula (I1), a monomer having a structure represented by formula (I2), and a monomer having a structure represented by formula (I3); the monomer B' is a monomer with a structure shown in a formula (II); the monomer C' is at least one selected from monomers having a structure represented by formula (III1) and a structure represented by formula (III 2);
the monomer A ', the monomer B ' and the monomer C ' are respectively used for leading the polymer to contain a structural unit A, a structural unit B and a structural unit C, wherein the structural unit A is at least one selected from structural units with a structure shown in a formula (11), a structure shown in a formula (12) and a structure shown in a formula (13); the structural unit B is a structural unit with a structure shown in a formula (2); the structural unit C is at least one selected from structural units having a structure represented by formula (31) and a structure represented by formula (32); the amount of the polymeric composition used is such that the resulting polymer has a weight average molecular weight of from 35 to 60 million;
wherein the definitions of the groups correspond to the same ones as defined in claim 1 or 2.
6. The method according to claim 5, wherein the monomer A' is at least one selected from the group consisting of a monomer having a structure represented by formula (I4), a structure represented by formula (I5), and a structure represented by formula (I6); the monomer B' is a monomer with a structure shown in a formula (IV); the monomer C' is at least one selected from the group consisting of monomers having a structure represented by formula (V1), a structure represented by formula (V2), and a structure represented by formula (V3);
7. the process according to claim 5 or 6, wherein the monomers A ', B ' and C ' are used in such an amount that the resulting polymer has a content of structural units A of from 53.4 to 84.6% by weight, based on the total weight of the polymer; the content of the structural unit B is 8.2-25.0 wt%; the content of the structural unit C is 7.1-21.6 wt%;
preferably, the polymeric composition is used in an amount such that the resulting polymer has a weight average molecular weight of from 40 to 60 million.
8. The method of any one of claims 5-7, wherein the co-solvent is selected from at least one of soluble salts,
preferably, the co-solvent is selected from at least one of ammonium chloride, sodium chloride and potassium chloride;
preferably, the chain transfer agent is selected from at least one of sodium formate, potassium formate, sodium acetate and potassium acetate;
preferably, the initiator is selected from at least one of azo-type initiators, peroxide-type initiators, and redox-type initiators; the azo initiator is selected from at least one of azobisisobutyramidine hydrochloride, azobisisopropylimidazoline hydrochloride, azobiscyanovaleric acid and azobisisopropylimidazoline; the peroxide initiator is at least one selected from hydrogen peroxide, ammonium persulfate, sodium persulfate and potassium persulfate; the redox initiator is at least one selected from persulfate-sulfite, persulfate-thiourea and persulfate-organic salt.
9. The method of any one of claims 5-8, wherein the polymerization conditions comprise: the temperature is 45-75 ℃, and the time is 7-10 h.
10. A polymer produced by the process of any one of claims 5 to 9.
11. Use of a polymer according to any of claims 1 to 4 and 10 in a drilling fluid.
12. A drilling fluid comprising a polymer as claimed in any one of claims 1 to 4 and 10.
13. The drilling fluid of claim 12, wherein the drilling fluid further comprises bentonite, calcium chloride, white bitumen, barite and water;
preferably, in the drilling fluid, relative to 100 parts by weight of water, the content of the bentonite is 1-2 parts by weight, the content of the calcium chloride is 10-15 parts by weight, the content of the white asphalt is 1-3 parts by weight, the content of the barite is 150-180 parts by weight, and the content of the polymer is 2.5-3 parts by weight.
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